Natural products continue to provide the drug discovery community with a nearly endless variety of biologically active lead compounds from which to develop medicines targeted to specific disease states. As our ability to synthesize complex molecules increases, it becomes increasingly important to develop syntheses which are able to access more than just a single target. Instead, creating routes where entire families of compounds can be generated provides far more value and allows for the increased exploration of chemical space around a given scaffold. However, to achieve the site-specific and chemoselective transformations needed in such an approach, increasingly better tools for C-H functionalization are required. The proposed research will develop the first concise and scalable route for the general synthesis of diterpenoid alkaloids. This class of compounds, which includes the clinically approved lappaconitine, displays a wide range of biological activity including analgesic, anti-inflammatory, antiarrhythmic, anesthetic, antithermic, antiparasitic, and antifeedant properties. The ability to access large quantities of various natural and unnatural diterpenoid alkaloids would greatly facilitate analog development and the possibility of discovering novel therapeutic agents. The proposed research also includes the development of a practical and preparative, intermolecular Hofmann-Lffler-Freytag reaction. The successful development of this reaction would be immediately useful to scientists as it would allow for the controlled, regioselective C-H halogenation of unactivated alkanes, the products of which are valuable chemical intermediates in the synthesis of medicines and materials.